Solid-state composition comprising solid particles and binder

ABSTRACT

Solid-state composition having a flexural strength of at least 0.5 N/mm 2 , which composition comprises from solid particles and a hydrocarbonaceous binder containing (i) from 15 to 95% by weight, based on total binder, of asphaltenes, which asphaltenes contain at least 60% aromatic carbon, and (ii) from 5 to 85% by weight, based on total binder, of further hydrocarbons, with the proviso that the solid particles are not solely carbon particles; process for preparing such composition, use of such composition in construction, construction element containing such composition and construction containing such construction elements.

This is a 371 filing of PCT/EP00/00734.

FIELD OF THE INVENTION

The present invention relates to solid-state compositions comprisingsolid particles and a hydrocarbonaceous binder. Further, the presentinvention relates to a process for preparing such composition, to theuse of such composition in construction, to a construction elementcontaining such composition, and to a construction containing suchconstruction elements.

BACKGROUND OF THE INVENTION

It is known to mix carbon particles such as petroleum coke, carbon blackor anthracite coal with binder materials such as coal tar pitch andpetroleum pitch, forming these mixtures by molding or extrusion andbaking the mixtures in furnaces at temperatures from 800-1400° C.(Kirk-Othmer Encyclopedia of Chemical Technology 3^(rd) edition, volume4, page 557).

U.S. Pat. No. 4,961,837 describes a specific petroleum pitch for bindingcarbon black to manufacture electrodes for the aluminium and steelindustries, which petroleum pitch has been obtained by pre-heating afeedstock, feeding the pre-heated feedstock to a soaker so as to promotecondensation and polymerisation, and separating off a petroleum tarpitch of a quality suitable for use as a binder in the manufacture ofelectrodes.

The teaching of both documents is limited to the use of these binderswith carbon particles.

U.S. Pat. No. 5,759,250 describes the use of a very hard bitumen binderfor road bed foundations. The bitumen preferably is a blend of bitumenobtained from a hard base produced by direct distillation and having apenetrability from 15 to 25 and a heavy fraction obtained bydistillation of crude petroleum or of products obtained by a processsuch as catalytic or thermal cracking. It is stated that these bitumenbinders can only be used in road bed foundation layers because they donot have sufficient adherence properties and asphalt prepared from itdoes not present a closed, smooth surface without holes and roughness.Further, it is described that these foundation layers must be covered bya top layer to ensure good thermal protection.

Surprisingly, we have now found binders which can be hard while havinggood adhesion properties.

Japanese laid open patent application No. 61-89215 describes a methodfor selectively separating high molecular weight polycyclic aromaticpolymer from residual oil produced by thermal cracking of naphtha. Thepolymer is described to be suitable as an auxiliary material formoulding sand to overcome the disadvantages of existing quartz powder.

The best model of the bonding action in moulding sand is that of awedge-and-block bond at the interface of the particles. The bondingaction is not that of a glue or adhesive causing the particles to adhereto each other (Kirk-Othmer Encyclopedia of Chemical Technology 3^(rd)edition, volume 6, page 213). Therefore, the flexural strength of amoulding sand approaches 0 N/mm². The compositions according to thepresent invention differ from moulding sands in that the compositionsaccording to the present invention have a flexural strength of at least0.5 N/mm².

SUMMARY OF THE INVENTION

The solid-state compositions according to the present invention have aflexural strength of at least 0.5 N/mm² and comprise from 70 to 99% byweight of solid particles and from 30 to 1% by weight of ahydrocarbonaceous binder, which binder contains (i) from 15 to 95% byweight, based on total binder, of asphaltenes, which asphaltenes containat least 60% aromatic carbon, and (ii) from 5 to 85% by weight, based ontotal binder, of further hydrocarbons, with the proviso that the solidparticles are not solely carbon particles.

The amounts of solid particles and hydrocarbonaceous binder are based onamount of total composition.

Hydrocarbonaceous binders according to the present invention, aregenerally considered waste products. They are usually thought unsuitablefor any attractive application other than as anode binder material or aspart of fuel oil.

Surprisingly, compositions according to the present invention wereobserved to have good flexural strength. Further, compositions accordingto the present invention were observed to retain their flexural strengthrelatively well after exposure to water optionally containing saltand/or acid.

It was further found that compositions according to the presentinvention could be made harder by keeping them at elevated temperatureeither by a dedicated heat treatment or by keeping them at elevatedtemperature during manufacture and/or hot storage. Furthermore, it wasfound that this increased the flexural strength of compositions.

The flexural strength is measured according to NEN 7014, “NederlandsNormalisatie Instituut”, 2^(nd) edition, August, 1974.

The amount of asphaltenes in the hydrocarbonaceous binder is determinedaccording IP 143/96.

The percentage of aromatic carbon atoms present in the asphaltenes ismeasured by separating off the asphaltenes in the binder as described inIP 143/96, dissolving a sample of the asphaltenes in carbon disulphideor chloroform and assessing the percentage of aromatic carbon by H and¹³CNMR.

The present invention further relates to a process for preparing acomposition according to the present invention, which process comprisesmixing from 70 to 99% by weight of solid particles and from 30 to 1% byweight of molten hydrocarbonaceous binder and allowing the resultingmixture to solidify, which binder contains (i) from 15 to 95% by weight,based on total binder, of asphaltenes, which asphaltenes contain atleast 60% aromatic carbon, and (ii) from 5 to 85% by weight, based ontotal binder, of further hydrocarbons, with the proviso that the solidparticles are not solely carbon particles.

The present invention further relates to the use of a compositionaccording to the invention in construction, to a construction elementcontaining such composition and to a construction containing suchconstruction elements.

DETAILED DESCRIPTION OF THE INVENTION

The solid-state composition according to the present invention compriseshydrocarbonaceous binder which contains from 15 to 95% by weight, basedon total binder, of asphaltenes as determined according IP 143/96. Theasphaltenes comprise hydrogen, carbon and optionally other atoms.Specifically, the asphaltenes can contain up to 15% by weight of atomsother than hydrogen and carbon, more specifically sulphur, nitrogen andoxygen, preferably at most 12% by weight, most preferably at most 10% byweight, based on asphaltenes.

The hydrocarbonaceous binder comprises from 5 to 85% by weight offurther hydrocarbons. The further hydrocarbons are compounds other thanasphaltenes as determined according IP 143/96. The further hydrocarbonscomprise hydrogen, carbon and optionally other atoms. Generally, thefurther hydrocarbons can contain up to 15% by weight of atoms other thanhydrogen and carbon, more specifically sulphur, nitrogen and oxygen,preferably at most 12% by weight, most preferably at most 10% by weight,based on further hydrocarbons.

Preferably, the binder contains at least 20% by weight of asphaltenes,based on total binder. More preferably, the hydrocarbonaceous bindercontains at least 25% by weight of asphaltenes. The amount ofasphaltenes is up to 95% by weight, preferably up to 70% by weight, morepreferably up to 60% by weight, more preferably up to 50% by weight,more preferably up to 45% by weight, most preferably at most 40% byweight. The remainder of the hydrocarbonaceous binder is furtherhydrocarbons.

The hydrocarbonaceous binder does not solely consist of carbon asproduced after full carbonization, e.g. by heat treating of a coal taror thermally cracked residual fraction.

Coal tar pitch differs from the present hydrocarbonaceous binder in thatcoal tar pitch contains a limited amount of asphaltenes. The amount ofasphaltenes in coal tar pitch typically is less than 10% by weight.Furthermore, coal tar pitch contains substantial amounts of hazardouspolyaromatic compounds containing 4 or 5 aromatic rings. The binder ofthe present invention will generally contain a very limited amount ofpolyaromatic compounds containing 4 or 5 aromatic rings. Generally, thebinder of the present invention will contain less than 2% by weight ofhazardous polyaromatic compounds containing 4 or 5 aromatic rings, morespecifically less than 1% by weight, more specifically less than 0.5% byweight. The amount of these polyaromatic compounds is based on amount ofbinder and is measured by high-resolution gas chromatography asdescribed in the article by J. Blomberg et al., Journal ofChromatography A, 849 (1999), pages 483-494.

The hydrocarbonaceous binder is present in an amount of from 1 to 30% byweight. Preferably, the hydrocarbonaceous binder is present in an amountof at least 2% by weight, more preferably in an amount of at least 3% byweight, most preferably at least 4% by weight. Preferably, thehydrocarbonaceous binder is present in an amount of up to 15% by weight,more preferably up to 10% by weight, most preferably up to 8% by weight.

The hydrocarbonaceous binder is desirably a binder which is solid at 20°C. and below. Generally, the hydrocarbonaceous binder will have avisco-elastic behaviour which is such that its penetration can bemeasured according to ASTM D 5 at 25° C. Preferably, thehydrocarbonaceous binder has a penetration of at most 30 dmm at 25° C.,more preferably at most 20, more preferably at most 15, more preferablyat most 10 dmm, most preferably less than 10 dmm. Further, thehydrocarbonaceous binder preferably has a penetration of at least 0.1dmm at 25° C., more preferably at least 1 dmm, more preferably at least2 dmm, most preferably at least 4 dmm.

The penetration values below 2 dmm can be measured by measuring at 40°C. and subsequently extrapolating the results.

The hydrocarbonaceous binder according to the present inventionpreferably has a softening point, measured according to the ring andball test of ASTM D 36, of at most 160° C., more preferably at most 150°C., more preferably at most 120° C., most preferably at most 100° C.

The hydrocarbonaceous binder can be prepared in any way obvious tosomeone skilled in the art, provided that the binder obtained meets therequirements.

The hydrocarbonaceous binder can be prepared by subjecting hydrocarbonsto thermal cracking. Preferably, a residual hydrocarbon fraction issubjected to thermal cracking. The thermally cracked product can be usedas such, or in combination with any other hydrocarbon fraction as longas the requirements are met.

Preferably, the hydrocarbonaceous binder consists at least partly ofproduct obtained by subjecting hydrocarbons to thermal cracking. Mostpreferably, the hydrocarbonaceous binder consists of product obtained bysubjecting hydrocarbons to thermal cracking. Although in such case partof the thermally cracked product can be used, the binder only containsproduct which has been thermally cracked.

Thermal cracking is preferably carried out by pre-heating a hydrocarbonfraction to a temperature of from 350 to 500° C., maintaining thepre-heated oil at such conditions as to cause thermal cracking andsubsequently separating off one or more light fractions. Thermalcracking of residual fractions usually involves a temperature of between300 and 600° C. The pressure can be in the range from 1 to 100×10⁵ N/m²(bar), preferably in the range from 2 to 20×10⁵ N/m² (bar). Thermalcracking is preferably carried out in a soaker. The thermally crackedproduct as such can be used as binder, or the binder can be only a partof the thermally cracked product. In the latter case, the binder isseparated from the thermally cracked product in any suitable way.Preferably, the binder is produced by separating off the light fractionsby flash distillation, more preferably by vacuum flash distillation.

Another process by which the hydrocarbonaceous binder can be obtainedcomprises subjecting a residual fraction to hydroconversion at atemperature in the range from 200 to 450° C. and a pressure in the rangefrom 50 to 200×10⁵ N/m² (bar), optionally preceded byhydrodemetallization. Preferably, the hydroconversion ishydrodesulphurization.

Furthermore, the hydrocarbonaceous binder can be obtained by mixingdifferent hydrocarbon fractions. An attractive method comprises mixing acomposition containing solid particles and hydrocarbons, e.g. oilpolluted soil or solids containing tar sands, with further hydrocarbonssuch that the final composition is a composition according to thepresent invention. The oil polluted soil is allowed to contain sand,stones and/or wood.

In principle, any suitable solid particles can be used in thecomposition of the present invention. The solid particles must bedifferent from the hydrocarbonaceous binder. Further, the solidparticles are not solely carbon particles.

A non-exhaustive list of solid particles which can be used comprisesmineral particles, cement, concrete dust, recycled asphalt, recycledtyres, clay, old sand, porous particles such as zeolite and perlite,shells, crushed shells, spent catalyst, organic waste such as leaves andbones, fly-ash, rubber, polymers and wood particles such as chips,flakes and/or fibres and metal particles such as alumina. Solidparticles which give especially good results are shells, mineralparticles and/or wood particles.

Preferably, the solid particles comprise at least 5% by weight ofinorganic compounds, which are compounds not containing carbon, based onamount of solid particles, preferably at least 10% by weight. Mostpreferably, the solid particles are inorganic compounds.

Preferably, the solid particles are a combination of particles having aparticle size of at most 63 micrometers (so-called filler) and particleshaving a particle size in the range from 63 micrometers to 2 mm(so-called sand) and particles having a particle size in the range from2 to 8 mm, preferably from 4 to 8 mm (so-called stones), optionally incombination with particles having larger sizes. The particle sizes aremeasured by sieving with sieves having openings of the indicated size.Preferably, the amount of each of filler, sand and stones is in therange from 10 to 50% by weight, (the combination to total 100% byweight) based on total amount of solid particles. Solid particles havinga particle size of more than 8 mm are preferably present if largerobjects are made.

Especially good results have been obtained with compositions comprisingsolid particles containing silica and/or alumina. It has been found thatsolid particles containing silica, give compositions of high flexuralstrength. Compositions containing solid particles containing alumina,were found having high compression strength. Preferably, thecompositions comprise from 1 to 100% by weight of silica and/or alumina,based on amount of solid particles, more preferably from 1 to 100% byweight of silica, more preferably from 5 to 90% of silica, morepreferably from 10 to 70% of silica.

It is especially preferred that the solid particles comprise quartz.Quartz consists of silica. Preferably, the compositions comprise from 20to 95% by weight of quartz, based on amount of solid particles, morespecifically from 30 to 90% by weight.

In order to make the composition electrically conductive, thecomposition can further contain electrically conductive solid particles,preferably graphite particles such as flakes or fibres. Preferably, thecomposition can comprise from 0 to 40% by weight of electricallyconductive solid particles, based on total composition, more preferablyfrom 5 to 20% by weight. By adjusting the amount of electricallyconductive material in the composition, it is possible to makecompositions ranging from electrically resistant compositions toelectrically conductive compositions.

Further, the composition according to the present invention, cancomprise magnetic materials such as iron particles. In this way, amagnetic composition can be obtained.

If the composition is to be used for heat insulation, the compositioncan contain solid particles increasing its heat insulation properties.If the composition is to be used for conducting heat, the compositioncan contain solid particles increasing its heat conductivity properties.If the composition is to be used for sound insulation or dampening, thecomposition can contain solid particles increasing its sound insulationand/or dampening properties.

If wood is present in the composition according to the presentinvention, the composition preferably comprises between 1 and 97% byweight of wood particles, based on total composition. The wood particlescan be present in the form of treated or untreated fibres, chips, flakesand/or powder. Such compositions are especially suitable for makingboards. Preferably, the composition comprises at least 5% by weight ofwood particles, preferably fibres, based on total composition, morepreferably at least 10% by weight. The composition preferably comprisesat most 80% by weight of wood particles, preferably fibres, morepreferably at most 70% by weight, based on total composition.

The composition of the present invention is solid at ambienttemperature. The combination of solid particles and hydrocarbonaceousbinder preferably becomes liquid at a temperature of 80° C. or more,more preferably 110° C. or more.

The compositions of the present invention have a flexural strength of atleast 0.5 N/mm². A good flexural strength is advantageous when using thecompositions in construction elements. Preferably, the flexural strengthis at least 3 N/mm², more preferably at least 4 N/mm², more preferablyat least 5 N/mm², most preferably at least 6 N/mm2. Flexural strength ismeasured according to NEN 7014, “Nederlands Normalisatie Instituut”,2^(nd) edition, August, 1974. For many applications low flexuralstrengths of at least 0.5 N/mm² suffice.

It has been found that good compression strengths can be obtained byusing the composition of the present invention. This is advantageouswhen using the composition in construction elements. Compressionstrengths which can be obtained are 5 N/mm² or more, preferably 10 N/mm²or more, more specifically 15 N/mm² or more, measured according to ISO/R836 of the European Federation of Manufacturers of Refractory Productsas revised in 1990, PRE/R 14-1. The presence of graphite has been foundto inrease the compression strength. However, for many applications suchhigh compression strengths are not necessary.

The compositions according to the present invention preferably have avoid content of at most 3%, more preferably at most 2.5%, mostpreferably at most 2.0%. The void content is determined according to the“Standaard Regelgeving Advisering Wegenbouw”, 1995, test 67. However,for many applications such low void contents are not necessary. One ofthe applications where compositions according to the present inventioncan have a high void content, are low density compositions. Thesespecific compositions have a density of at most 1000 kg/m³.

It was observed that compositions according to the present inventioncould be made harder by keeping them at elevated temperature either by adedicated heat treatment or by keeping them at elevated temperatureduring manufacture and/or hot storage. A test for this specific kind ofhardening is RTFOT (ASTM D 2872). In some tests, the penetration of acomposition according to the present invention was as low as 50% or lessof the original penetration value. Further, it was observed that theflexural strength increased by the heat treatment.

The heat treatment can involve heating the compositions to a temperatureof at least 70° C., preferably at least 100° C., more preferably atleast 130° C., more preferably at least 150° C., more preferably atleast 200° C. during at least 0.25 hour, more preferably at least 0.5hour, more preferably at least 1 hour. The temperature is preferably atmost 300° C., and the time is preferably at most 3 hours. Althoughhigher temperatures and longer times can be applied, this is usually notattractive for economic reasons.

In order to further improve the properties of the hydrocarbonaceousbinder, the composition of the present invention can containconventional additives for increasing hardness, flexural strength and/oradhesion. Preferably, the composition according to the present inventioncomprises up to 3% by weight of iron and/or one or more iron containingcompounds, based on amount of hydrocarbonaceous binder, more preferablyfrom 0.001 to 1% by weight. Most preferably, the iron salt is ironoxide. The iron and/or iron compound can simultaneously act as pigment.

Further, radical forming compounds can be incorporated in a compositionaccording to the present invention in order to accelerate hardening.Compounds which can be incorporated are polymers such as polyethene and(spent) catalyst fines.

The composition of the present invention can comprise further compoundsto change the properties of the final product and/or to facilitatemanufacture of the composition and/or final product. A non-exhaustivelist of further compounds which can be present comprises heavyparaffins, sulphur, polyethylene, polypropylene, ethylene vinyl acetate,elastomers and polymers containing available epoxy groups as describedin WO 96/28513.

The appearance of compositions of the present invention can be changedas desired for its application. In order to change the colour of thecompositions, any of the conventional pigments can be used. In order toobtain a smoother surface, the surface of the compositions can betreated with a flame or the sizes of the solid particles can beadjusted, as known to someone skilled in the art. In order to improvethe appearance of compositions, more specifically of constructionelements, the surface can be treated with wax or wax like materials suchas bees wax, petroleum wax, synthetic wax or silicones containingpolish.

The composition of the present invention can be prepared in any suitableway. Optionally, the hydrocarbonaceous binder can be made into asuspension or emulsion which is subsequently mixed with the solidparticles. Preferably the solid particles will be mixed with moltenhydrocarbonaceous binder, e.g. a hydrocarbonaceous binder containing therequired asphaltenes is melted, and mixed with either cold or warm solidparticles, or hot solid particles are mixed with hot or coldhydrocarbonaceous binder. Additionally, a molten hydrocarbonaceousbinder can be mixed with solid particles, and the required asphaltenescan be formed in-situ during thermal treatment of the mixture.

An advantageous method of preparing compositions or constructionelements according to the present invention, comprises using thehydrocarbonaceous binder, optionally together with solid particles, inthe form of binder containing particles, more specifally in the form ofbinder containing granulate or powder. Either none, part or all of thesolid particles can be present in the binder containing particles.Binder containing particles are easy to use in transport and duringmanufacture. The use of binder containing particles is especiallyadvantageous if the binder is relatively hard, i.e. has a relatively lowpenetration, in which case the particles will not stick together. Suchbinder containing particles can contain further additives such aspigments.

The composition of the present invention is especially suitable for usein construction, including building. Therefore, the present inventionfurther relates to construction elements comprising compositionaccording to the present invention. Composition according to the presentinvention is especially suitable to replace concrete. A constructionelement is a self-contained component of fixed dimensions, which is usedin construction. Construction elements include building elements.Preferred construction elements are pipes, tiles, roof tiles, pavingstones (pavers), flagstones, bricks, foundations, boards, gutters and/orconduits. Road surfaces, floors and roofs are not construction elements.Preferably, the construction element will have dimensions of at most 5meters by at most 5 meters by at most 40 meters, more specificallydimensions of at most 1 meter by at most 1 meter by at most 2 meters.Preferably, the element will have dimensions of at most 1 meter by atmost 1 meter by at most 0.5 meter. Most preferably, the element willhave dimensions of at most 20 centimeter by at most 20 centimeter by atmost 10 centimeter. The construction element preferably is a block.Compositions according to the present invention are especially suitablefor use in paving stones in view of the good flexural strength of thecompositions, especially the good flexural strength retained afterhaving been exposed to water optionally containing salt and/or (strong)acid, more especially such exposure at elevated temperature.

Construction elements containing composition according to the presentinvention, have the further advantage that they can be recycled.

The present invention further relates to constructions, includingbuildings, comprising construction elements according to the presentinvention

Due to their stability, the compositions and construction elements ofthe present invention are especially suitable for use outdoors.

In order to increase the load-carrying properties, the compositions cancontain reinforcements such as steel bars, steel fabric, polymers, glassfibres, carbon fibres, carbon flakes and/or carbon fabric.

EXAMPLES

The flexural strength in all examples was measured according to NEN 7014test of the “Nederlands Normalisatie Instituut”, 2^(nd) edition, August,1974.

The compression strength was measured according to ISO/R 836 of theEuropean Federation of Manufacturers of Refractory Products as revisedin 1990, PRE/R 14-1.

The void content was determined according to the “Standaard RegelgevingAdvisering Wegenbouw”, 1995, test 67.

The “Marshall method” applied has been described in “StandaardRegelgeving Advisering Wegenbouw”, 1995, test 47 (pages 111-119) withthe difference that the particle size distribution of each batch ofsolid particles was measured and the different batches were combined toobtain the desired particle size distribution, instead of separating themineral aggregate into separate fractions.

The asphaltenes were separated off as described in IP 143/96.

The amount of aromatic carbon in the asphaltenes was determined by H and¹³CNMR measurements.

The penetration was measured according to ASTM D 5 at 25° C.

Example 1

A hydrocarbonaceous binder was obtained by thermal cracking of aresidual fraction of Middle East origin having a boiling point of 520°C. or more, and subsequently removing the light fractions by subjectingthe product to vacuum flashing. The binder obtained would have a boilingpoint of 520° C. or more under atmospheric conditions.

The hydrocarbonaceous binder contained 24.9% by weight of asphaltenes.The asphaltenes had 64.6% by weight of carbon atoms in aromatic rings.The hydrocarbonaceous binder contained 75.1% by weight of furtherhydrocarbons. The hydrocarbonaceous binder had a penetration of 7 dmm.

The hydrocarbonaceous binder (7.68% by weight) was melted and heated toa temperature of 180° C. and mixed with 20.27% by weight of filler(particle size less than 63 micrometer), 39.86% by weight of sand(particle size, between 63 micrometers and 2 mm), and 39.87% by weightof stones (particle size between 4 and 8 mm, broken Dutch river gravel),all amounts based on total weight of solid particles. The mineralparticles were preheated to a temperature of 180° C.

Mixing was carried out with a mixing apparatus ex Hobart for 3 minutesat 180° C.

1.1 kg of this mix having a temperature of 180° C. was placed in apreheated (180° C.) mould of 8 centimeter height and 10.5 centimeterdiameter, and cylindrical blocks were prepared according to the Marshallmethod.

Discs of 8 mm thickness sawn from these cylindrical blocks, were usedfor testing.

The flexural strength of a disc was 7.4 N/mm². The voids content was2.3%.

Further discs were aged by storing them in 1 M HCl or 1 M NaCl solutionsfor 1-9 weeks.

After 3 weeks in 1 M HCl solution at ambient temperature the flexuralstrength was 4.7 N/mm².

After 9 weeks in 1 M HCl solution at ambient temperature, the flexuralstrength was 4.3 N/mm².

After 1 week 1 M NaCl solution at 60° C., the flexural strength was 4.7N/mm².

Example 2

Hydrocarbonaceous binder was mixed with the preheated mineral particlesas described in Example 1 except that the mix had a temperature of 210°C.

Blocks were prepared as described in the Marshall method.

The flexural strenght was about 4 N/mm².

The compression strength of the blocks was 19 N/mm².

Example 3A

4 kg of the mix of hydrocarbonaceous binder and mineral particlesprepared as described in example 1 and having a temperature of 180° C.was placed in a conventional cement concrete tile (flagstone) mould(200×200×80 mm), which mould was at ambient temperature. Tiles wereprepared with a conventional tile production machine at a compactiontime of 12 seconds.

The flexural strength of the tiles was 8.1 N/mm² and the void contentwas 2.4%.

Example 3B

4 kg of the mix of hydrocarbonaceous binder and mineral particlesprepared as described in example 1 except that the mix had a temperatureof 200° C., was placed in a conventional cement concrete paving stone(paver) mould (200×100×80 mm) which mould was at ambient temperature.Paving stones were prepared with a conventinonal paving stone productionmachine at a compaction time of 12 seconds.

The flexural strength was 6.1 N/mm².

Example 3C

A paving stone, prepared as described in example 3B, was heated again to200° C. and mixed and placed in a paving stone mould to again prepare apaving stone, according to the method described in example 3B. Theflexural strength was found to be 6.3 N/mm².

This procedure was repeated again, resulting in a twice recycled pavingstone with a flexural strength of 6.7 N/mm².

Example 4 Comparative

A bitumen binder was obtained by subjecting a crude oil of Middle Eastorigin to distillation at atmospheric pressure, followed by subjectingthe residue obtained to distillation under reduced pressure. The residueobtained after distillation under reduced pressure would have a boilingpoint of 520° C. or more under atmospheric conditions, and had apenetration of 80-100 dmm and a content of asphaltenes of 11%. Theasphaltenes contained 53% of aromatic carbon. This binder was melted andused for preparing a mix at a temperature of 150-160° C. The mixcontained 7.1% by weight filler, 36.8% by weight sand, 56.1% by weightstones and 5.8% by weight binder, all amounts based on total weight ofsolid particles.

1.1 kg of this mix was used for the preparation of cylindrical blocks bythe Marshall method.

The flexural strength of a disc of 8 mm thickness sawn from the block,was 1.3 N/mm².

The compression strength of a block was 3.7 N/mm².

Example 5 Comparative

A bitumen binder was obtained by subjecting a crude oil of Americanorigin to distillation at atmospheric pressure, followed by subjectingthe residue obtained to distillation under reduced pressure. The residueobtained after distillation under reduced pressure would have a boilingpoint of 520° C. or more under atmospheric conditions, and had apenetration of 23 dmm and a content of asphaltenes of 11%. Theasphaltenes contained 35% of aromatic carbons.

This binder was melted and used for preparation of a mix as described inexample 1, except that the temperature of the mix was 170° C. 1.1 kg ofthis mix was used for the standard preparation of blocks according tothe Marshall method.

The flexural strength of a disc of 8 mm thickness sawn from this blockwas 3.2 N/mm². The void content was 2.8%.

Example 6 Comparative

A crude oil of Middle East origin was subjected to distillation underatmospheric pressure, followed by subjecting the residue obtained todistillation under reduced pressure. The residue obtained afterdistillation under reduced pressure would have a boiling point of 520°C. or more under atmospheric pressure. This residue was subjected toextraction with propane. The binder obtained had a penetration of 7 dmmand had a content of asphaltenes of 13.2% by weight. The binder wasmelted and used for preparing a mix containing 7.1% by weight filler,36.8% by weight sand, 56,1% by weight stones and 5.8% by weight ofbinder, all based on total amount of solid particles.

1.1 kg of this mix was used for preparing blocks according to theMarshall method. A block was used for compression strength measurement,giving a value of 11.6 N/mm².

Discs of 8 mm thickness sawn from these cylindrical blocks, were usedfor testing.

The flexural strength of a disc was 7.5 N/mm². The voids content was5.6%.

Further discs were aged by storing them in 1 M HCl or 1 M NaCl solutionsfor 1-9 weeks.

After 3 weeks in 1 M HCl solution at ambient temperature the flexuralstrength was 2.9 N/mm².

After 1 week 1 M NaCl solution at 60° C., the flexural strength was 3N/mm².

Example 7 Comparative

7.68% by weight of a binder as described in example 6, was mixed with20.4% by weight filler, 40.11% by weight sand, and 39.5% by weight puresilica stones (4-8 mm), all based on total amount of solid particles.

1.1 kg of this mix was used for the preparation blocks according to theMarshall method.

A disc of 8 mm thickness was sawn from the block and was found to have aflexural strength of 7 N/mm²

Another disc of 8 mm thickness was stored for 24 hours in seawater at atemperature of 60° C. after which the flexural strength was 3.7 N/mm².

Example 8

The hydrocarbonaceous binder as described in example 1, was used forpreparation of the mix as described by example 7.

1.1 kg of this mix was used for preparation of blocks according to theMarshall method.

A disc of 8 mm thickness was sawn from the block. The disc had aflexural strength of 7 N/mm² and a void content of 1%. The compressionstrength of a block was 12.8 N/mm².

Another disc of 8 mm thickness was stored for 24 hours in seawater at atemperature of 60° C. after which the flexural strength was 6.4 N/mm².

Example 9 Comparative

A bitumen binder was obtained by subjecting a crude oil of Americanorigin to distillation at atmospheric pressure, followed by subjectingthe residue obtained to distillation under reduced pressure. The residueobtained after distillation under reduced pressure would have a boilingpoint of 520° C. or more under atmospheric conditions, and had apenetration of 6 dmm and a content of asphaltenes of 22%. Theasphaltenes contained 53.6% of aromatic carbons. The binder was meltedand used for preparation of a mix with a filler, sand and stones asdescribed in example 1. 1.1 kg of this mix was used for preparing blocksaccording to the Marshall method.

A disc of 8 mm thickness was sawn from a block and had a flexuralstrength of 5.6 N/mm² and a voids content of 2.6%.

Example 10 Comparative

A bitumen binder was obtained by subjecting a crude oil of Far Eastorigin to distillation under atmospheric pressure, followed bysubjecting the residue obtained to distillation under reduced pressure.The residue obtained after distillation under reduced pressure wouldhave a boiling point of 520° C. or more under atmospheric conditions,and had a penetration of 5 dmm, contained 10.3% by weight ofasphaltenes. The asphaltenes contained 57.9% of aromatic carbon.

1.1 kg of the mix was melted and used for the preparation of blocksaccording to the Marshall method as described in example 1.

A disc of 8 mm thickness sawn from the block, had a flexural strength of2.4 N/mm² and 3.3% voids.

Example 11

The hydrocarbonaceous binder as described in example 1, was used forpreparing a mix containing 7.5% by weight binder, 7% by weight redpowder (iron oxide), 15.15% by weight of filler 38.92% by weight ofsand, and 38.93% by weight of stones, all based on total weight of solidparticles described in example 1.

1.1 kg mix was used for the preparation of Marshall method.

A disc of 8 mm thickness was sawn from the block for flexural strengthtesting giving a value of 7.3 N/mm².

The disc had a voids content of 1.8%.

Example 12

The hydrocarbonaceous binder as described in example 1, was used forpreparing a mix as described in example 1 in which the filler wasreplaced by red powder (20.27% by weight).

1.1 kg of mix was used for the preparation of blocks according to theMarshall method.

The flexural strength was about 4 N/mm2.

The compression strength was 20 N/mm2.

Example 13

The hydrocarbonaceous binder as described in example 1, was used forpreparing a mix of 7.97% by weight hydrocarbonaceous binder, 37.6%recycled asphalt, 21% by weight of filler and 41.4% by weight of sand,all based on total weight of solid particles. The mix was preparedaccording to the procedure described in example 1.

1.1 kg of mix was used for the preparation of blocks according to theMarshall method.

A disc of 8 mm thickness was sawn from a block and had a flexuralstrength of 7.2 N/mm² and 1.2% voids.

Example 14

The hydrocarbonaceous binder described in example 1, was used forpreparation of a mix having the following composition: 7.95% by weighthydrocarbonaceous binder, 17.4% graphite flakes, 41.3% by weight ofsand, and 41.3% by weight of stones all based on total weight of solidparticles. Mixed according to the procedure described in example 1, 1.1kg of mix was used for the preparation of blocks according to theMarshall method.

A disc of 8 mm thickness was sawn from a block and had a flexuralstrength of 3.5 N/mm².

The electrical restitivity was 20Ω.

Example 15

The hydrocarbonaceous binder described in example 1, was used forpreparation of a mix having the following composition: 7.8% by weighthydrocarbonaceous binder, 8.5%w graphite flakes, 10.29% by weight offiller, 40.61% by weight of sand, and 40.58% by weight of stones, allbased on total weight of solid particles. Mixed according to theprocedure described in example 1, 1.1 kg of mix was used for preparationof blocks according to the Marshall method.

A disc of 8 mm thickness sawn from a block, had a flexural strength of6.2 N/mm2 and 3% voids.

The electrical restitivity was 200Ω.

Example 16

The hydrocarbonaceous binder as described in example 1, was used forpreparation of a very open composition comprising 6.43% by weightbinder, 5.8% by weight of filler, 10.13% by weight of sand and 84.07% byweight of stones, all based on total weight of solid particles. Mixedaccording to the procedure described in example 1, 1.1 kg of mix wasused for the preparation of blocks according to the Marshall method.

The flexural strength was estimated to be 2 N/mm2.

The compression strength was 7.6 N/mm².

Example 17 Comparative

A hydrocarbonaceous binder was obtained by thermal cracking of aresidual fraction of Middle East origin having a boiling point of 520°C. or more, and subsequently removing the light fractions by subjectingthe product to vacuum flashing. The binder obtained would have a boilingpoint of 520° C. or more under atmospheric conditions.

The hydrocarbonaceous binder had a penetration of 47 dmm and contained12.6% by weight of asphaltenes. The binder was used in the preparationof a mix as described in example 1.

1.1 kg of this mix was used for preparing blocks according to theMarshall method.

A disc of 8 mm thickness was sawn from a block. The flexural strengthwas 3.6 N/mm².

The compression strength of a block was 5.9 N/mm².

The Examples according to the invention show that compositions accordingto the present invention have a good flexural strength.

Comparison of Example 1 with Example 6 (comparative), and comparison ofExample 7 (comparative) with Example 8, shows that compositionsaccording to the present invention retain their flexural strength betterafter exposure to water containing NaCl and after exposure to watercontaining HCl, than compositions not according to the invention.

Examples 3B and 3C show that the flexural strength of compositionsaccording to the present invention, increases by heat treatment.

What is claimed is:
 1. Solid-state composition having a flexuralstrength of at least 0.5 N/mm², which composition comprises from 70 to99% by weight of solid particles and from 30 to 1% by weight of ahydrocarbonaceous binder, which binder contains (i) from 15 to 95% byweight, based on total binder, of asphaltenes, which asphaltenes containat least 60% aromatic carbon, and (ii) from 5 to 85% by weight, based ontotal binder, of further hydrocarbons, with the proviso that the solidparticles are not solely carbon particles.
 2. Composition according toclaim 1, which composition has a flexural strength of at least 3 N/mm².3. Composition according to claim 1, in which composition thehydrocarbonaceous binder has a penetration of at most 10 dmm. 4.Composition according to claim 1, which hydrocarbonaceous binderconsists of product obtained by subjecting hydrocarbons to thermalcracking.
 5. Composition according to claim 1, which hydrocarbonaceousbinder consists of product obtained by pre-heating a hydrocarbon oil toa temperature of from 350 to 500° C., maintaining the pre-heated oil atsuch conditions as to cause thermal cracking and subsequently separatingoff one or more light fractions.
 6. Composition according to claim 1,which composition comprises from 1 to 100% by weight of silica, based onamount of solid particles.
 7. Process for preparing a solid-statecomposition according to claim 1, which process comprises mixing from 70to 99% by weight of solid particles and from 30 to 1% by weight ofmolten hydrocarbonaceous binder, which binder contains (i) from 15 to95% by weight, based on total binder, of asphaltenes, which asphaltenescontain at least 60% aromatic carbon, and (ii) from 5 to 85% by weight,based on total binder, of further hydrocarbons, and allowing theresulting mixture to solidify, with the proviso that the solid particlesare not solely carbon particles.
 8. Construction element comprising acomposition according to claim
 1. 9. Construction element according toclaim 8, which element has dimensions of at most 1 meter by at most 1meter by at most 2 meters.
 10. Construction containing constructionelements according to claim 8.